HF alkylation process

ABSTRACT

A novel liquid acid catalyzed alkylation process is disclosed which incorporates a fixed bed of contact material to improve the alkylation reaction zone efficiency. The fixed bed of contact material also allows the process to be efficiently operated at lower acid to olefin mole/mole feed ratios than normally used.

BACKGROUND OF THE INVENTION

This invention relates to an improved process for the alkylation of a hydrocarbon substrate with an olefin alkylating agent in the presence of a liquid alkylation catalyst. The process utilizes a fixed bed of contact material in the alkylation reaction zone to improve the process efficiency. The process efficiency improvement allows the process to be operated at lower acid to olefin feed ratios with a resulting decrease in the volume of dangerous acid required for processing.

The alkylation of a hydrocarbon substrate with an olefin alkylating agent in the presence of a liquid acid catalyst is a well known method of producing high octane gasoline boiling range products, linear alkylbenzene compounds, and alkylaromatics, among other useful products. A continuing goal in the art is to provide an economically attractive and intrinsically safe acidcatalyzed alkylation process.

The acid utilized in alkylation typically poses great environmental and health risks. Any reduction in required process volumes, storage volumes, etc. is highly desired.

OBJECTS AND EMBODIMENTS

It is therefore an object of the present invention to provide an improved process for the liquid acid-catalyzed alkylation of a hydrocarbon substrate with an olefin acting agent. The acid alkylation process of the instant invention is able to efficiently produce an alkylation product utilizing much less acid catalyst in the feed than conventional acid alkylation processes.

Accordingly, the present invention is a process for the liquid phase alkylation of an olefin acting agent with a hydrocarbon substrate in the presence of an acid alkylation catalyst. The process comprises the steps of admixing a reaction mixture comprising the olefin acting agent, the hydrocarbon substrate, and the acid alkylation catalyst in an alkylation reaction zone operating at alkylation reaction conditions. The alkylation reaction zone is characterized in that it contains a fixed bed of particulate contact material which occupies a portion to all of the volume of the reaction zone. The reaction mixture is passed through the fixed bed of particulate contact material and into a separator. In the separator, the acid catalyst is separated from the product hydrocarbons. The product hydrocarbons are withdrawn from the separator and further processed to separate and recover the product hydrocarbons. The acid catalyst recovered from the separator is recycled back to the alkylation reaction zone.

This is well as other objects and embodiments will become apparent upon review of the following, more detailed description of the prior art and the invention.

INFORMATION DISCLOSURE

The new of a fixed bed of contact material in an alkylation process catalyzed with liquid acid is heretofore unknown. The use of solid supported catalysts for hydrocarbon alkylation has been disclosed. U.S. Pat. No. 3,678,120 discloses a catalytic composite comprised of an inert solid support combined with either antimony pentafluoride, hydrogen fluoride, fluosulfonic acid, or mixtures thereof. The U.S. Pat. No. 3,618,120 also discloses the use of the catalyst in a fixed bed catalytic process for the alkylation or isomerization of hydrocarbons.

Many other hydrocarbon alkylation processes employing a fixed bed of a solid catalystic composite are known. For instance, U.S. Pat. No. 4,116,880 discloses an alkylation process and catalyst. The catalyst is comprised of fluorinated graphite along with a Lewis acid selected from the halides of the elements of Group II-A, III-A, IV-B, V, or VI-B of the Periodic Table. U.S. Pat. No. 4,083,885 discloses a process for the alkylation of a hydrocarbon using a fixed bed of catalyst. The fixed bed of catalyst is comprised of graphite intercalated with from 5 to 50 wt. % of a Lewis acid fluoride. Other alkylation processes employing fixed beds of solid supported alkylation catalysts are disclosed in U.S. Pat. Nos. 3,852,371 and 3,979,476.

U.S. Pat. No. 3,839,487 discloses a process for alkylating a paraffin with an olefin. The process is accomplished by introducing the hydrocarbon and liquid acid catalyst at separate points on a plurality of linear fibers in a reaction zone. This patent describes a process performing a function in a similar manner as that of the instant process. However, the U.S. Pat. No. 3,839,487 does not in any manner describe the process of the instant invention or the benefits of the process of the instant invention, namely that a mixture of alkylatable hydrocarbons can be efficiently alkylated with a small amount of liquid acid catalyst by performing the process in a reaction zone containing a fixed bed of inert particulate contact material.

DESCRIPTION OF THE DRAWING

The drawing represents a preferred embodiment of the flow scheme of the process of this invention. A first hydrocarbon feed comprising an olefinacting agent such as a C₂ -C₂₀ olefinic hydrocarbon is introduced into the reaction zone 6 through line 1. A second hydrocarbon feed stream comprising a hydrocarbon substrate such as an isoparaffin or benzene is introduced into the reaction zone 6 through line 13. The hydrocarbon substrate of line 13 consists of fresh hydrocarbon substrate from line 2 combined with recycle hydrocarbon substrate from line 4. The final feed component to the reactor zone 6 comprises a liquid acid alkylation catalyst which is introduced into the reaction zone through line 14. The liquid acid catalyst of line 14 is comprised of a mixture of fresh liquid acid catalyst from line 3 mixed with recycle liquid acid catalyst from line 5.

The three feed components form an emulsion type admixture in the reaction zone 6. The admixture passes through a fixed bed of contact material 7, within the reaction zone 6 with the contact material improving the contacting between the liquid acid catalyst and the two hydrocarbon feedstocks. After a reactor residence time of from 2.0 to 60.0 hr⁻¹, the admixture exits the reaction zone 6 through line 8.

The reaction zone effluent passes through line 8 into a separator vessel 9. In the separator vessel 9, the hydrocarbons are separated from the liquid acid alkylation catalyst. The liquid acid alkylation catalyst is recycled through line 5 to the reaction zone, while the hydrocarbon phase is directed through line 10 to the separation zone 11.

The separation zone 11 can be configured in any manner such that the desired produce and recycle hydrocarbons are recovered in essentially pure form. The product hydrocarbon of the separation zone 11 are recovered through line 12 while the recycle hydrocarbon substrate is recycled to the reaction zone through line 4.

This drawing is a schematic outline of the basic method of this invention. It is not intended to place any limitation on the scope or practice of the invention or to exclude the large number of variations in this general flow scheme which are apparent to those skilled in the art. Various required subsystems such as pumps, valves, control systems, fractionators, and the like have been deleted for the purposes of simplicity and clarity of presentation.

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to a process for alkylating a reaction mixture comprising an olefin acting agent and a hydrocarbon substrate with a liquid acid alkylation catalyst such as sulfuric acid or hydrofluoric acid in an alkylation reaction zone containing a fixed bed of inert particulate contact material. Hydrocarbon substrates which may be alkylated in the process of the present invention include paraffinic and aromatic hydrocarbons. Typical paraffins include isobutane and higher homologues having a tertiary carbon atom, such as 2-methylbutane and 2,4-dimethylpentane. Other alkylatable materials include benzene, toluene, xylene, naphthenes, phenols, cresols, amines, thiophenes, and isoparaffinic mercaptans.

It is preferred that the hydrocarbon substrate is either isobutane or benzene.

Olefin acting agents also comprise a feed component to the process of the instant invention. Suitable olefin acting agents are typically straight or branched hydrocarbons containing one or more carbon-carbon double bond. It is preferred that the olefin acting agent contain from 2 to 20 carbon atoms, and it is most preferred that the olefin acting agent contain from 3 to 5 carbon atoms.

The alkylation reaction is promoted through the presence of a liquid acid alkylation catalyst such as hydrofluoric acid, sulfuric acid, phosphoric acid, and the like, or mixtures thereof. These acids are maintained in a liquid phase containing a minimum of water to reduce corrosion problems. The catalyst may also comprise a mixture of a mineral acid with a Friedel-Crafts metal halide such as aluminum chloride, aluminum bromide, boron trifluoride, and other proton donors.

Additionally, it is anticipated that the liquid acid alkylation catalyst of the instant invention may contain compounds such as surfactants, alcohols, MTBE, and the like liquid compounds known to assist in the promotion of acid catalyzed alkylation process. Furthermore, it is anticipated that the process of the present invention may be accomplished with any liquid acid alkylation catalyst known in the prior art. It is preferred however that the liquid acid alkylation catalyst is either sulfuric acid or hydrofluoric acid.

Alkylation conditions in general include a pressure sufficient to maintain the hydrocarbons and acid in a liquid phase, with a general range being from about 1 to 40 atmospheres. The alkylation reaction may take place at temperatures of from 0°-390° C. with a range from 0°-275° C. being more preferred. The reaction also occurs at liquid hourly space velocities ranging from 0.1 to 100 hr⁻¹ and preferably at a space velocity of from 0.5 to 60 hr⁻¹.

Another important alkylation reaction process variable is the molar ratio of the hydrocarbon substrate to the olefin acting agent. As known to those skilled in the art, typical alkylation zone conditions necessarily include a high ratio of the molar concentration of the hydrocarbon substrate to the molar concentration of the olefin acting agent in order to produce a high quality alkylate product. A broad range of this ratio is from about 3 to about 20 with a preferred operating range being from 5 to 16.

A second and very important feed ratio of the process of the present invention is the molar ratio of the liquid acid alkylation catalyst to the olefin acting agent being fed to the alkylation reaction zone. The minimization of this ratio is an important aspect of the process of the instant invention. A low molar ratio of acid catalyst to olefin acting agent means less acid catalyst is required in the process. It also means that a smaller supply of acid is required to maintain acid inventory. By minimizing this ratio, the volume of acid catalyst necessary is minimized resulting in a reduction in the potential environmental and safety dangers posed by the acid catalyst. Thus, for this process, the acid to olefin molar feed ratio may vary from 0.01 to 100; however, a ratio in the range of 0.05 to 10 is most preferred for safety purposes.

It is preferred that the liquid acid catalyzed alkylation process of the instant invention be used to produce a high octane motor fuel product. To accomplish this, it is preferred that the feedstock to the process comprise a C₃ -C₅ olefinic hydrocarbon, an isoparaffin, and hydrofluoric acid. Optimum reaction zone conditions for the production of a motor fuel alkylate from these feed components includes a temperature of from 0° to 50° C., a pressure of from 1 to 20 atmospheres, a liquid hourly space velocity of from 2 to 60 hr⁻¹, and a hydrofluoric acid to C₃ -C₅ olefin molar feed ratio of from 0.05 to 10. This feed ratio corresponds to an HF to C₃ -C₅ olefin volumetric feed ratio of from about 0.1 to 16.7.

A general flow of an alkylation process designed for the production of high octane number motor fuel comprises the steps of contacting a mixture of the two hydrocarbons to be reacted with a liquid mineral acid-catalyst, mixing the reactants and the acid in the reaction zone to form an emulsion, allowing the emulsion to soak for a length of time during which some agitation oro turbulence is maintained to sustain the emulsion, passing the emulsion into a setting zone in which separate liquid acid and hydrocarbon phases form, and withdrawing the separate liquid phases from the settling zone. It is common practice, at this point, to recirculate at least a portion of the acid phase to the reaction zone. This recirculated acid is often cooled so that it functions as a heat sink for the exothermic reaction. A large amount of unreacted isoparaffins or aromatics is present in the withdrawn hydrocarbon phase. This material may be recovered from the separated liquid hydrocarbon phase by such methods as flashing or fractionation and also recirculated to the reaction zone. Some processes do not utilize a soak zone at all and still others contact the separated hydrocarbon phase with a regenerated high strength acid stream to aid in acid removal.

The reaction vessel used to practice this invention can be any type of vessel constructed to withstand the pressure, temperature, and corrosive conditions of an acid catalyzed alkylation operation, but is preferably a cylindrical steel vessel being relatively elongated and vertically positioned. The top and bottom walls of the receiving vessel can be flat plates or can be spherically shaped caps. For purposes of description, the receiving vessel may be divided into upper and lower sections, generally equal to the upper and lower half respectively of the vessel. Preferably, however, the upper section comprises the upper quarter of the vessel while the lower section comprises the lower quarter of the vessel. The feed inlet means are preferably vertically positioned tubes which are located in the upper or lower section of the receiving vessel so that their respective outlets discharge a nondispersed high velocity stream of unreacted hydrocarbons in an upward or downward direction. The fluid standpipe can be one or more small diameter vertical pipes which pass through the receiving vessel and which may be connected to a manifold arrangement used for distribution of the hydrocarbon through the standpipes. The standpipe may have a nozzle located on its outlet, and more than one standpipe may be utilized.

It is an important aspect of the process of the present invention that the reaction zone contain a fixed bed of inert particulate contact material. The fixed bed of particulate contact material should be uniform in depth and cover the entire cross-section of the reactor vessel. The fixed bed of inert contact material should fill from 10% to 100% of the reactor volume. The inert particulate contact material may be in the form of tablets, extrudates, spheres, or randomly shaped naturally occurring pieces. An 8×20 mesh material is especially suitable. Natural materials such as clays and silicates or refractory inorganic oxides may be used as the inert contact material. The material may therefore be formed from diatomaceous earth, kieselguhr, kaolin, alumina, zirconia, etc. It is especially preferred that the catalyst comprises a carbon-containing support, particularly charcoals which have been thermally and/or chemically treated to yield a highly porous structure similar to activated carbon, or activated carbon itself.

The bed of particulate contact material is very useful in the process of the present invention. The inert bed of contact material improves the efficiency of the alkylation reaction resulting in increased desired product yield at constant reaction conditions. The efficiency improvement gained from the use of the bed of inert contact material allows the process to be operated at a lower acid to olefin feed ratio while maintaining standard product quality.

It is believed that the fixed bed of inert contact material improves the efficiency of the alkylation reaction by assisting in the maintaining of the hydrocarbon, liquid acid emulsion. Further, the inert bed of contact material provides an extended surface upon which the two immiscible liquids may react. It is believed that particulate contact materials with high surface areas are most useful in the instant process.

In the description of the preferred embodiments herein provided, it is intended that both the alkylation reactor and a reaction soaker, if one is utilized, are included within the scope of the term "alkylation reaction zone". Suitable reaction soakers are well known in the art. For example, the reaction soakers described in U.S. Pat. Nos. 3,560,587 and 3,607,970 may suitably be employed in the present process. Such reaction soakers are conventionally vessels equipped with perforated trays, baffle sections, or the like to maintain an alkylation reaction mixture in the form of a fairly homogeneous mixture, or emulsion, for a predetermined length of time. The alkylation reaction mixture of catalyst and hydrocarbons is maintained in the reaction soaker for a time which depends on the composition of the reaction mixture. Generally, a reaction soaker residence time of about 1 minute to about 30 minutes is employed. The temperature and pressure maintained in the reaction soaker are substantially the same as the temperature and pressure maintained in the associated alkylation reactor.

Means for settling the reaction mixture effluent from the alkylation reaction zone in order to separate a settled hydrocarbon phase and the liquid acid catalyst phase are well known in the alkylation art. Generally, the effluent alkylation reactor mixture recovered from an alkylation reactor or soaker comprises a mixture of unreacted hydrocarbons, alkylation reaction products, acid catalyst, and catalyst-soluble organic materials, possibly with small amounts of light hydrocarbons, etc. When this alkylation reaction mixture is allowed to stand unstirred, i.e., settled, the alkylation reaction products, hydrocarbon substrate, and light hydrocarbons form a lighter settled hydrocarbon phase. The acid catalyst phase comprising the liquid acid catalyst forms a separate phase. The settled hydrocarbon phase is then simply mechanically separated from the catalyst phase. The temperature and pressure maintained during such a settling operation are substantially the same as those described above in connection with the alkylation conditions employed in the reaction zone. The hydrocarbons and the catalyst are preferably in the liquid phase during the settling separation operation.

Some means for withdrawing heat from alkylation zone may be necessary for optimum operation of the process. A variety of means for accomplishing the heat withdrawal are well known. For example, the heat generated in the alkylation reaction may be withdrawn from the alkylation reactor by indirect heat exchange between cooling water and the reaction mixture in the reactor.

It is also an aspect of the alkylation process of the instant invention that the hydrocarbon phase recovered from the separator be further fractionated to purify product and feed hydrocarbons for recovery or recycle purposes. It is also an aspect of the process of the instant invention that the liquid acid catalyst recovered from the separator be recycled back to the alkylation reaction zone directly, or be purified or regenerated by means known in the art before being recycled to the alkylation reaction zone.

In order to demonstrate the benefits and advantages of the present invention in contrast to prior art alkylation methods, the following example is offered. It is to be understood that this example is intended to be illustrative and in no way restrictive on the otherwise broad embodiments of the present invention as set forth in the claims appended hereto.

EXAMPLE

This example was conducted in a pilot plant scale unit operation. The pilot plant comprised a monel autoclave in which an isoparaffin and olefin-acting agent are contacted with a once-through stream of hydrofluoric acid catalyst. After sufficient time, the hydrocarbon and acid phases are removed from the autoclave and passed to a settler in which the phases are allowed to separate. The hydrocarbon phase comprising alkylate is removed from the settler and passed to neutralization facilities. Thereafter, the hydrocarbon phase is collected for analysis.

In this example, five different runs were made in the pilot plant. The first two runs were at different acid to olefin molar feed ratios and used a reactor with no packing. The third and fourth runs employed a reactor with 10 and 30 vol. % of activated carbon packing at an acid to olefin molar feed ratio of 7. The fifth test utilized 30 vol. % of activated carbon packing and an alkylation catalyst containing 5.0 wt. % MTBE (methyl tert-butylether).

In all four runs, the processing conditions were identical, and comprised a temperature of 20° C., a pressure of 8.8 atmospheres, a residence time of 10 minutes, and a stirring rate of 1800 rpm. The volumetric ratio of the acid phase feed rate to the olefin feed rate was held at 57 to the first run and at 7.0 for all other runs. The mole ratio of isobutane to C₄ olefins was 7.5. The C₄ olefin molar distribution was 46.9% 2-butene, 34.8% 1-butene, and 28.3% isobutylene.

In each run, the alkylate product was analyzed and the products were found to have the compositions and research octane numbers as set forth in Table 1 below.

                  TABLE 1                                                          ______________________________________                                         Conditions        Feedstock                                                    ______________________________________                                         Temp. - 20° C.                                                                            i-C.sub.4 /C.sub.4.sup.=  (mole/mole) = 7.5                  Pressure - 8.85 atm                                                                              C.sub.4.sup.=  - 2/C.sub.4.sup.=  -1/iC.sub.4.sup.=  =                         46.9/34.8/28.3 (mol. %)                                      Stirring Rate - 1800 rpm                                                                         HF/C.sub.4.sup.=  (mole/mole):7                              ______________________________________                                                                                95% HF                                  Catalyst:    HF      HF      HF   HF   5% MTBE                                 ______________________________________                                         HF/C.sub.4.sup.=  (mole/mole)                                                               57      7       7    7    7                                       Packing, Vol. %                                                                             None    None    10%  30%  30%                                     Alkylate Yield, %                                                                           99.1    99.4    99.7 99.5 99.6                                    Alkylate                                                                       Composition, Wt. %:                                                            C.sub.8.sup.-                                                                               7.9     7.5     7.5  7.9  8.2                                     TMP          70.2    66.2    66.8 68.8 69.6                                    DMH          16.0    20.7    20.1 18.0 16.1                                    C.sub.8.sup.+                                                                               5.9     5.6     5.6  5.3  6.1                                     RON          93.2    90.8    91.0 91.9 92.7                                    ______________________________________                                    

The results set forth in the Table indicate that product octane (RON) increases with increasing volumes of reactor packing. The addition of an MTBE component results in an even greater octane improvement. The octane improvement is explained by comparing the amount of TMP (trimethylpentane) to DMH (dimethylhexane) produced in each run. TMP has an octane value of 103 while DMH has an octane value of 70 on average. Thus, the conditions which produce larger amounts of TMP in comparison to DMH will typically result in a product with a higher octane value.

The first run mimics an alkylation process utilizing a typical HF/C₄ =(mole/mole) feed ratio of 57. The octane of a product produced by this feedstock is 93.2. When the HF/C₄ =(mole/mole) feed ratio is dropped to 7, the product octane also falls to 90.8. Adding packing to the reactor at the low feed acid to olefin feed ratio results in an octane of 91.0 at 10% reactor packing volume, and a 91.9 octane at a 30% reactor packing volume. Pilot plant constraints prevented the evaluation of larger packing volumes at the lower acid to olefin molar feed rate, but the trend indicates that the product octane rises with increased reactor packing volumes. The example therefore shows that a product octane essentially equivalent to that produced at high acid to olefin feed ratios is obtainable at low acid to olefin feed rates by utilizing a reactor packing comprising a particulate contact material. 

What is claimed is:
 1. A process for the liquid phase alkylation of an olefin acting agent with a hydrocarbon substrate in the presence of a liquid acid alkylation catalyst which comprises the steps of:(a) introducing reactants comprising an olefin acting agent, a hydrocarbon substrate, and a liquid acid alkylation catalyst into an alkylation reaction zone operating at alkylation reaction conditions and containing a fixed bed of activated carbon to create a reaction mixture; (b) passing the reaction mixture through the fixed bed of activated carbon in the alkylation reaction zone, and out of the reaction zone and into a separator; (c) separating the acid alkylation catalyst from the product and unreacted feed hydrocarbons; (d) withdrawing the hydrocarbons from the separator and purifying and recovering the product hydrocarbons and the unreacted hydrocarbons of the liquid phase alkylation reaction; and (e) recycling at least a portion of the separated acid alkylation catalyst back to the alkylation reactor inlet.
 2. The process of claim 1 further characterized in that the acid alkylation catalyst comprises sulfuric acid.
 3. The process of claim 1 further characterized in that the acid alkylation catalyst comprises hydrofluoric acid.
 4. The process of claim 3 further characterized in that the olefin acting agent comprises a C₂ -C₂₀ olefinic hydrocarbon.
 5. A process for the liquid phase alkylation of a C₂ -C₂₀ olefinic hydrocarbon with a hydrocarbon substrate in the presence of hydrofluoric acid which comprises the steps of:(a) introducing reactants comprising C₂ -C₂₀ olefinic hydrocarbons, a hydrocarbon substrate and hydrofluoric acid into an alkylation reaction zone to create a reaction mixture where the alkylation reaction zone is at alkylation reaction conditions including a temperature of from 0°-275° C., a pressure of from 1 to 40 atmospheres, a hydrofluoric acid to olefinic hydrocarbon molar feed ratio of from 0.01 to 100, and a reactor space velocity of from 0.5 to 60 hr⁻¹, and where the alkylation reaction zone contains a fixed bed of activated carbon; (b) passing the reaction mixture through the fixed bed of activated carbon in the alkylation reaction zone, out of the reaction zone and into a separator; (c) separating the hydrofluoric acid catalyst from the product and unreacted feed hydrocarbons; (d) withdrawing the hydrocarbons from the separator and purifying and recovering the product hydrocarbons and the unreacted hydrocarbons of the liquid phase alkylation reaction; and (e) recycling at least a portion of the separated hydrofluoric acid to the inlet of the alkylation reactor.
 6. The process of claim 5 further characterized in that the hydrocarbon substrate comprises benzene.
 7. The process of claim 5 further characterized in that the hydrocarbon substrate comprises an isoparaffin.
 8. The process of claim 7 further characterized in that the C₂ -C₂₀ olefinic hydrocarbons comprise C₃ -C₅ olefins.
 9. The process of claim 8 further characterized in that the fixed bed of activated carbon occupies from 10% to 100% of the reactor void volume.
 10. A process for the liquid phase alkylation of a C₃ -C₅ olefinic hydrocarbon with an isoparaffin in the presence of hydrofluoric acid which comprises the steps of:(a) introducing reactants comprising C₃ -C₅ olefins, isoparaffins, and hydrofluoric acid into an alkylation reaction zone containing 10-100% by volume of a fixed bed of activated carbon to create a reaction mixture and where the alkylation reaction zone is at alkylation reaction conditions including a temperature of from 0° to 50° C., a pressure of from 1 to 20 atmospheres, a hydrofluoric acid to C₃ -C₅ olefin molar feed ratio of from 0.05 to 10.0, and a reactor space velocity of from 2.0 to 60.0 hr⁻¹ ; (b) passing the reaction mixture through the fixed bed of activated carbon in the alkylation reaction zone and out of the reaction zone and into a seaprator; (c) separating the hydrofluoric acid from the product and unreacted feed hydrocarbons of the reaction mixture; (d) withdrawing the hydrocarbons from the separator and purifying and recovering the product hydrocarbon and unreacted hydrocarbon of the liquid phase alkylation reaction; and (e) recycling at least a portion of the separated hydrofluoric acid to the inlet of the alkylation reactor.
 11. The process of claim 10 further characterized in that the hydrofluoric acid alkylation catalyst comprises from 0.1 to 5.0 vol. % MTBE. 